WO2012148085A2 - Antimony amino alkoxide compound and method for preparing same, and method for forming a thin film containing antimony using the antimony amino alkoxide compound and an atomic layer deposition technique - Google Patents

Abstract

The present invention relates to a novel antimony amino alkoxide compound and to a method for preparing a thin film containing antimony using same. The novel antimony amino alkoxide compound according to the present invention may be expressed as Sb[O-A-NR1R2]3, where A is a linear or branched C2-C5 alkylene optionally substituted with a C1-C10 alkyl group; and R1 and R2 are an independent linear or branched C1-C10 alkyl group, respectively. According to the present invention, it is possible to provide an antimony precursor enabling a thin film of superior quality to be prepared.

Description

Antimony amino alkoxide compound and manufacturing method thereof, Formation method of thin film containing antimony using this antimony amino alkoxide compound and using atomic layer deposition technique

The present invention relates to a novel antimony amino alkoxide compound and a method for preparing the same, and a method for producing a film containing antimony using atomic layer deposition techniques using the antimony amino alkoxide compound.

Antimony trioxide (Sb2O3) has been widely applied in the fields of catalysts, electrical conductor materials, optical materials, flame retardants, etc. (Kokkalas, DE, Bikiaris, DN, Karayannidis, GP, J. Appl. Poly. Sci. 2003, 55, .787; Bryngelsson, Hl, Eskhult, J., Nyholm, L., Herranen, M ,, Alm, O., Edstram, K., Chem. Mater. 2007, 19, 1170; Tigau, N., Ciupina , V., Prodan, GJ Optoelectro., Adv. Mater. 2006, 8, 37; Ballistreri, A., Foti, S., Montaudo, G., Pappalardo, S., Scamporrino, E., J Poly. Sci. Poly.Chem.Ed. 2003, 17, 2469; Brebu, M., Jakab, E., Sakata, Y., J. Anal.Appl.Pyrolysis, 2007, 79, 346; Papaspyrides, CD, Pavlidou, S., Vouyiouka, SN, J. Mate.Design.Appl. 2009, 223, 91).

Meanwhile, with the development of information technology, various electronic devices are increasing. In particular, portable media devices have become high performance and large in capacity to store and provide various information. There is a need for a highly integrated memory device for storing and transferring large amounts of data using such media devices. The highly integrated memory device has not only large capacity but also satisfies various conditions such as high speed, nonvolatile and economic efficiency such as low power consumption. Currently widely used DRAM and flash memory devices can satisfy some of the conditions mentioned above.

However, since the DRAM unit cell includes one capacitor and one transistor for controlling the capacitor, a relatively large unit cell area is required as compared to the NAND flash memory having a string structure. Also, the DRAM is a volatile memory device that loses stored data when power supply is interrupted. On the other hand, flash memory is a nonvolatile memory device that does not lose its stored data even when its power supply is interrupted. However, the flash memory is slow in operation because it is based on a tunneling phenomenon.

Accordingly, research on a phase change memory device is increasing as a next-generation memory having a high operation speed and nonvolatile characteristics. The unit cell of the phase change memory device may include a phase change material as an element for storing data. The phase change material may have states with different resistance values. For example, the phase change material in the crystalline state may have a lower resistance value than the phase change material in the amorphous state. The crystal state of the phase change material can be controlled through the conditions of the melting and cooling process. With regard to the physical and structural problems of phase change memory devices, development of manufacturing processes of phase change memory devices is required.

In a phase change chalcogenide non-vaporizable memory technique using germanium-antimony-tellurium (Ge2Sb2Te5) membranes, antimony is used as a key component along with germanium and tellurium. Phase-change random access memory (PRAM) devices based on Ge-Sb-Te (GST) thin films utilize a reversible transition from a crystalline state to an amorphous state associated with the resistive change of the membrane material. For commercial high speed manufacturing and performance reasons, the film material itself is preferably formed using methods such as chemical vapor deposition (CVD) and atomic layer deposition (ALD).

Despite their prospects, there are practical problems faced with efforts to grow high quality antimonide, Sb2Te3 and GST films that are reproducible via CVD and ALD at low temperatures. Only a very limited number of antimony CVD / ALD precursors are currently available, most of which are alkyl-based compounds such as Me3Sb, Et3Sb, (iPr) 3Sb and Ph3Sb or hydride-based compounds such as SbH3 and these precursors have low thermal stability, low vaporization, There are various drawbacks, including difficulty in synthesis and high delivery temperatures. (Sugiura, 0., Kameda, H., Shiina, K., Mataumura, M., J. Electron. Mater., 1988, 17, 11 .; Biefeld, RM, Hebner, GA, Appl. Phys. Lett. 1990 , 57, 1563; Stauf, GT, Gaskill, DK, Bottka, N., Gedridge, RW Jr., Appl.Phys. Lett. 1991, 58, 1311.)

In addition, the compatibility of these currently available antimony precursors with germanium or tellurium precursors has not been confirmed in terms of the ability to reproducibly grow microelectronic device quality GST films, and the growth of antimonide films is sensitive to V / III ratios and decomposition temperatures. Has associated process difficulties. Deposition metal films formed from such precursors are susceptible to precursor-derived carbon or heteroatomic contaminants that can result in low growth rates, poor morphology, and film composition variations (Korean Patent Publication No. 10-2009-0091107).

 In general, the synthesis of a compound having high volatility is the most important problem in order to design and synthesize a thin film or a precursor for nanomaterials.

As described above, the antimony trivalent compounds known in the art have problems such as insufficient volatility, supply of oxygen from the outside, contamination of carbon and chlorine generated in the prepared membrane, and the like. Therefore, the development of the antimony trivalent compound as a precursor that can be used in the production of antimony and antimony trioxide thin film is highly significant.

In addition, GST film manufacturing processes of conventional PRAMs known in the art are manufactured by sputtering method, which is physical vapor deposition, or by using CVD, which is chemical vapor deposition. However, such a method cannot secure uniformity of the GST film and causes problems such as a short channel effect.

For this reason, there have been attempts to apply the ALD process, but it was difficult to produce a GST thin film by the ALD process because the antimony precursor, especially the antimony precursor, used in the conventional GST film production is difficult to apply to the ALD process.

It is an object of the present invention to provide a novel antimony amino alkoxide having excellent thermal stability and volatility and having an advantageous preservation, and a method for preparing the same.

It is also an object of the present invention to provide novel antimony amino alkoxide compounds which are capable of producing pure antimony or antimony trioxide at low temperatures and which do not contain halogen elements and methods for their preparation.

In addition, an object of the present invention is to produce a thin film of excellent quality, in particular a novel antimony amino alkoxide compound capable of growing the thin film also by organic metal chemical vapor deposition (MOCVD) or atomic layer deposition (ALD) and its preparation To provide a way.

In addition, an object of the present invention is to provide a method for producing an antimony thin film by the ALD process using the antimony precursor suitable for the ALD process.

It is another object of the present invention to provide an antimony thin film produced by the ALD process.

The present invention provides an antimony amino alkoxide compound represented by Formula 1:

<Formula 1>

Sb [O-A-NR1R2] 3

In Chemical Formula 1,

A is C2-C5 alkylene unsubstituted or substituted with a C1-C10 linear or branched alkyl group;

R1 and R2 are each independently a C1-C10 linear or branched alkyl group.

The present invention provides a method for preparing an antimony amino alkoxide compound represented by the following Chemical Formula 1, comprising reacting an antimony halide compound represented by the following Chemical Formula 3 with an alkali metal salt of an alcohol represented by the Chemical Formula 4.

<Formula 3>

SbX3

<Formula 4>

M [O-A-NR1R2]

In Formula 1, Formula 3 and Formula 4,

A is C2-C5 alkylene unsubstituted or substituted with C1-C10 linear or branched alkyl groups;

R 1 and R 2 are, independently from each other, a C 1 -C 10 linear or branched alkyl group;

M is Li, Na or K;

X is Cl, Br or I.

The present invention comprises the steps of preparing an antimony compound represented by the following formula (6) by reacting the antimony halide compound of formula 3 and the alkali metal compound represented by the formula (5) in an organic solvent; And it provides a method for producing an antimony amino alkoxide compound of formula (1) comprising the step of reacting the antimony compound represented by the formula (6) and the alcohol represented by the formula (7) in an organic solvent.

<Formula 1>

Sb [O-A-NR1R2] 3

<Formula 3>

SbX3

<Formula 5>

M [NR52]

<Formula 6>

Sb [NR52] 3

<Formula 7>

HO-A-NR1R2

In Chemical Formula 1, Chemical Formula 3, Chemical Formula 5, Chemical Formula 6, and Chemical Formula 7,

A is C2-C5 alkylene unsubstituted or substituted with a C1-C10 linear or branched alkyl group;

R 1 and R 2 are each independently C 1 -C 10 linear or branched alkyl groups;

R5 is a C1-C10 linear or branched alkyl group, or SiR63, and R6 is a C1-C10 linear or branched alkyl group;

M is Li, Na or K;

X is Cl, Br or I.

It is an object of the present invention to provide a method for forming a thin film, wherein the antimony amino alkoxide compound is used as a precursor to form a thin film containing antimony.

Method for producing an antimony thin film according to the present invention for achieving the above object comprises the steps of preparing a substrate in a vacuum chamber;

Preparing an antimony precursor material;

Preparing a source gas from the antimony precursor material;

Preparing a reaction gas including hydrogen gas;

Preparing a purge gas;

Preparing a metal precursor gas from the metal precursor material; And

And performing a one-cycle process of sequentially supplying the source gas, the reaction gas, the purge gas, and the metal precursor gas into the vacuum chamber to form an antimony-metal monolayer layer thin film on the substrate.

The antimony precursor material is characterized in that the antimony amino alkoxide represented by the formula (1).

In the method for manufacturing the antimony thin film, it is preferable to repeat the step of forming an antimony-metal monolayer thin film on the substrate to control the thickness of the thin film.

The substrate is preferably maintained in a temperature range of 60 ℃ to 160 ℃.

Preferably, the purge gas is argon.

Preferably, the metal is telluride.

In the one-cycle process of sequentially supplying the source gas, reaction gas, purge gas and the metal precursor gas into the vacuum chamber, further supplying a first plasma after supplying the source gas, and the metal precursor And further supplying the second plasma after supplying the gas.

The antimony precursor is preferably a compound represented by the following formula (2).

<Formula 2>

Sb [O-CR ³ R ⁴ (CH ₂ ) m-NR ¹ R ² ] ₃

In Chemical Formula 2,

R ³ and R ⁴ are each independently C ₁ -C ₁₀ linear or branched alkyl groups;

m is an integer of 1-3.

In Chemical Formula 2,

R ¹ , R ² , R ³ and R ⁴ are each independently methyl, ethyl, n-propyl, i-propyl or t-butyl;

It is preferable that said m is 1 or 2.

Antimony thin film according to the present invention for achieving the above object is characterized in that it is produced by the above method.

Since the novel antimony precursor according to the present invention binds to an oxygen atom ligand, it is advantageous for the production of a thin film containing antimony.

In addition, since the novel antimony precursor according to the present invention binds to amino alkoxides, the thermal stability and the volatility are excellent, and thus the preservation is excellent.

In addition, the novel antimony precursor according to the present invention can produce a thin film of excellent quality, and can be particularly useful when manufacturing a thin film by organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).

 In addition, the antimony thin film can be produced at a low temperature by the ALD process, thereby improving the mass productivity.

1 is a result of 1 H NMR analysis of Sb (dmamp) 3 compound prepared in Example 1.

FIG. 2 is a 13C NMR spectrum of Sb (dmamp) 3 compound prepared in Example 1. FIG.

3 is a graph showing the results of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of the Sb (dmamp) 3 compound prepared in Example 1.

Figure 4 is a 1H NMR analysis of the Sb (dmamb) 3 compound prepared in Example 3.

5 is a 13C NMR spectrum of a Sb (dmamb) 3 compound prepared in Example 3. FIG.

Figure 6 is a graph showing the results of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of the Sb (dmamb) 3 compound prepared in Example 3.

7 is a graph illustrating a correlation between a growth rate and a growth temperature for manufacturing an antimony thin film according to an embodiment of the present invention.

Figure 8a shows an SEM image of the antimony thin film prepared at 60 ℃ in accordance with an embodiment of the present invention, b is a SEM image of the antimony thin film prepared at 80 ℃ in accordance with an embodiment of the present invention , c shows the SEM image of the antimony thin film prepared at 100 ℃ according to an embodiment of the present invention.

FIG. 9 is a graph showing the XRD diffraction pattern pumice results of the antimony thin film manufactured according to an embodiment of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention provides an antimony amino alkoxide compound represented by the following formula (1).

<Formula 1>

Sb [O-A-NR1R2] 3

In Formula 1, C2-C5 alkylene unsubstituted or substituted with a linear or branched alkyl group of C1-C10; R1 and R2 are each independently a C1-C10 linear or branched alkyl group.

The form of the antimony amino alkoxide compound represented by Formula 1 is not particularly limited, but is preferably in a liquid state.

The antimony amino alkoxide compound represented by Formula 1 may be an antimony amino alkoxide compound represented by Formula 2 below.

<Formula 2>

Sb [O-CR3R4 (CH2) m-NR1R2] 3

In Chemical Formula 2,

R1, R2, R3 and R4 are each independently a C1-C10 linear or branched alkyl group, preferably R1, R2, R3 and R4 are each independently methyl, ethyl, n-propyl, i-propyl or t- Butyl.

And m is an integer of 1-3, Preferably it is 1 or 2.

The antimony amino alkoxide compound represented by Chemical Formula 1 according to the present invention may be prepared by the following two methods.

In the first method, the antimony amino alkoxide compound represented by Formula 1 according to the present invention is prepared by reacting an antimony halide compound represented by Formula 3 with an alkali metal salt of an alcohol represented by Formula 4. The reaction scheme may be represented by the following scheme 1.

<Formula 3>

SbX3

<Formula 4>

M [O-A-NR1R2]

In Chemical Formulas 3 and 4,

M is Li, Na or K; X is Cl, Br or I.

Substituents, which are not otherwise described, have the same description as in Formula 1 above.

The antimony halide compound represented by Chemical Formula 3 and the alkali metal salt of the alcohol represented by Chemical Formula 4 are preferably reacted in the presence of an organic solvent, preferably 12 to 36 hours at room temperature. The organic solvent is not particularly limited as long as it is used in the art, but hexane, toluene, ethyl ether, tetrahydrofuran, and dichloromethane may be used.

<Scheme 1>

SbX3 + M [O-A-NR1R2] → Sb [O-A-NR1R2] 3

In the second method, the antimony amino alkoxide compound represented by Chemical Formula 1 according to the present invention is reacted with an antimony halide compound represented by Chemical Formula 3 and an alkali metal compound represented by Chemical Formula 5 under an organic solvent to be represented by Chemical Formula 6 below. Preparing an antimony compound; And reacting an antimony compound represented by the following Chemical Formula 6 with an alcohol represented by the following Chemical Formula 7, preferably 3 equivalents in an organic solvent. The reaction scheme may be represented by the following scheme 2.

<Formula 5>

M [NR52]

<Formula 6>

Sb [NR52] 3

<Formula 7>

HO-A-NR1R2

In Chemical Formula 5, Chemical Formula 6, and Chemical Formula 7,

R5 is a C1-C10 linear or branched alkyl group, or SiR63, and R6 is a C1-C10 linear or branched alkyl group; M is Li, Na or K; X is Cl, Br or I.

Substituents not otherwise described are the same as those of Formulas 1 to 3.

The organic solvent is not particularly limited as long as it is used in the art, but hexane, toluene, ethyl ether, tetrahydrofuran, and dichloromethane may be used.

<Scheme 2>

SbX3 + M [NR52] → Sb [NR52] 3 + HO-A-NR1R2 → Sb [O-A-NR1R2] 3

On the other hand, the present invention provides a method for forming a thin film, using the antimony amino alkoxide compound represented by the formula (1) as a precursor to form a thin film containing antimony.

Here, the antimony thin film is preferably formed by organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).

Since the novel antimony precursor according to the present invention binds to an oxygen atom ligand, it is advantageous for the production of a thin film containing antimony. In addition, since the novel antimony precursor according to the present invention binds to amino alkoxides, the thermal stability and the volatility are excellent, and thus the preservation is excellent. In addition, the novel antimony precursor according to the present invention can produce a thin film having excellent quality, and can be usefully used when preparing a thin film by organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).

In particular, in the antimony precursor of the present invention, when the non-polar alkyl group is bonded to the a-carbon position with respect to the alkoxide oxygen, the affinity for the organic solvent is high, and the stereometal is prevented from causing intermolecular interaction with the oxygen of the neighboring ligand. It can be present as a monomer because of its disability. Due to these structural features, the antimony precursor of the present invention is a stable liquid at room temperature, has high solubility in organic solvents such as benzene, tetrahydrofuran, toluene, chloroform, and the like, and is highly volatile and does not contain a halogen element. Therefore, these can be used to obtain a thin film containing antimony having better quality.

The present invention also relates to a method for producing an antimony thin film using an ALD process and an antimony thin film produced thereby.

Method for producing an antimony thin film of the present invention comprises the steps of preparing a substrate in a vacuum chamber;

Preparing an antimony precursor material;

Preparing a source gas from the antimony precursor material;

Preparing a reaction gas including hydrogen gas;

Preparing a purge gas;

Preparing a metal precursor gas from the metal precursor material; And

And performing a one-cycle process of sequentially supplying the source gas, the reaction gas, the purge gas, and the metal precursor gas into the vacuum chamber to form an antimony-metal monolayer layer thin film on the substrate.

The antimony precursor material is a method for producing an antimony thin film, characterized in that the antimony amino alkoxide represented by the following formula (1):

<Formula I>

Sb [OA-NR ¹ R ² ] ₃

Wherein A is C ₂ to C ₅ alkylene unsubstituted or substituted with a C ₁ to C ₁₀ linear or branched alkyl group;

R ¹ and R ² are each independently a C ₁ to C ₁₀ linear or branched alkyl group.

ALD process is an abbreviation of Atomic Layer Depostion and is an atomic layer deposition process using nano thin film deposition technology using the phenomenon of monoatomic layer that is chemically attached. Since the film can be formed at a lower temperature than chemical vapor deposition, it is understood as a suitable technology for system-on-chip.

Although it may be applied to the manufacturing process of the GST thin film for PRAM, precursors that can be deposited at low temperatures are required to be applied to the ALD process. Application of the ALD process was difficult due to the difficulty in low temperature deposition of the precursor material, particularly the antimony precursor, required to prepare the GST thin film.

In the present invention, by applying to the ALD process using an antimony precursor of Formula 1, to form a thin film containing antimony. The antimony precursor of the formula (1) is bound to the oxygen atom ligand, it is assumed that it is advantageous for the production of antimony thin film.

First, prepare a substrate in a vacuum chamber. The substrate may be a known substrate that can be used in a semiconductor process, for example, a silicon substrate, a silicon dioxide substrate and the like. The silicon substrate can be, for example, an amorphous silicon or a polycrystalline silicon substrate.

When the substrate is prepared in the vacuum chamber, it is heated so that the temperature of the substrate in the chamber is a temperature suitable for forming an antimony film.

When the substrate is heated up to a desired process temperature, an antimony film is formed by the ALD method. The process temperature of the substrate is preferably 60 to 160 ° C., and is preferably kept within this temperature range while the reaction continues.

If the temperature is outside this range, no reaction occurs or unwanted reactions interfere with the formation of the antimony atomic layer.

However, the present invention is not limited thereto, and even when the process temperature is relatively low or high, antimony atoms may be deposited by increasing the reaction rate by controlling other process variables such as pressure and flow rate of the source gas.

Then, a source gas is prepared from the antimony precursor material and supplied into the chamber to form an antimony layer having a predetermined thickness of an antimony atomic layer on the substrate.

Here, the antimony precursor of the formula (1) is used as the antimony precursor, preferably Sb [O-CR ³ R ⁴ (CH ₂ ) m-NR ¹ R ² ] ₃ of the formula ( ₂ ).

In this formula, R ³ and R ⁴ are each independently a C ₁ -C ₁₀ linear or branched alkyl group; m is an integer of 1-3. More preferably R ¹ , R ² , R ³ and R ⁴ are each independently methyl, ethyl, n-propyl, i-propyl or t-butyl; It is preferable that said m is 1 or 2.

When supplying the antimony precursor material into the chamber, an inert gas, such as argon, may be used as a carrier gas as necessary, but the carrier gas that can be used is not limited thereto.

After the antimony precursor material is fed into the chamber, a plasma may be optionally fed into the chamber to facilitate the reaction.

Then, a reaction gas is supplied on the antimony atomic layer formed on the substrate to provide antimony-presite on the surface of the antimony atomic layer. Hydrogen gas may be supplied as the reaction gas, but is not necessarily limited thereto.

Then, purge gas is supplied into the chamber to perform the purge process. An inert gas such as argon gas may be used as the purge gas, but is not limited thereto.

Then, a gas formed of a metal precursor material to be combined with antimony is supplied.

When supplying the metal precursor material into the chamber, an inert gas such as argon may be used as the carrier gas as necessary, but the carrier gas that can be used is not limited thereto.

After the metal precursor material has been fed into the chamber, a plasma can optionally be fed into the chamber to facilitate the reaction.

The metal may use telluride, but is not limited thereto. Telluride is a component of the GST film, which is a phase change layer of PRAM, and shows that when antimony and telluride are prepared using the ALD process, the entire GST film can be prepared by the ALD process.

One cycle of sequentially supplying source gas, reaction gas, purge gas, and metal precursor gas into a vacuum chamber is performed to form an atomic layer of antimony-metal on the substrate, and then cycled so that the thickness of the thin film becomes a desired thickness. Can be performed multiple times.

After forming a thin film of a desired thickness, an exhaust process is performed from the chamber to remove deposition byproducts remaining in the chamber.

According to the antimony thin film manufacturing method, it is possible to provide an antimony thin film having improved flatness of the surface layer of the thin film using an ALD process at low temperature, and in particular, to provide an antimony-telluride layer, and ultimately, GST for PRAM It is useful for film formation.

Hereinafter, the present invention will be described in detail by the following examples. However, the following examples are only to explain the present invention in more detail, and the scope of the present invention is not limited to the following examples.

Example

Preparation Example of Antimony Amino Alkoxide

All experiments were performed in an inert argon or nitrogen atmosphere using a glove box or Schlenk line. The structure of the reaction product was analyzed using proton nuclear magnetic resonance spectroscopy (1H NMR), carbon atom nuclear magnetic resonance spectroscopy (13C NMR) and thermogravimetric analysis / differential thermal analysis (TGA / DTA). .

Example 1 Synthesis of Tris [1-dimethylamino-2-methyl-2-propoxy] antimony [Sb (dmamp) 3] I

To a 125 mL Schlenk flask, SbCl 3 [2.0 g, 8.8 mmol] and Na (dmamp) [1-dimethylamino-2-methyl-2-propoxy sodium, 3.66 g, 26.3 mmol] were added followed by hexane (100 mL). Was added. The mixed solution was stirred at room temperature for one day, the solution was filtered and the solvent was removed under reduced pressure. The resulting liquid was purified by vacuum distillation (120 ° C / 10-2 Torr) to give an antimony compound bonded with three amino alkoxides represented by the formula (1) as a colorless liquid (3.2 g, yield 77.7%).

1 H NMR (C 6 D 6, 300.13 MHz): 1.50, (s, 12H, OC (CH 3) 2), 2.25 (s, 4H, NCH 2 C), 2.45 (s, 12H, N (CH 3) 2).

13 C NMR (C 6 D 6, 75.47 MHz): 33.2, 47.1, 70.7, 74.8.

Example 2 Synthesis of Tris [1-dimethylamino-2-methyl-2-propoxy] antimony [Sb (dmamp) 3] II

SbCl 3 [2.0 g, 8.8 mmol] and Li (btsa) [lithium bistrimethylsilylamide, 4.4 g, 26.3 mmol] were added to a 125 ml Schlenk flask, and toluene (100 ml) was added thereto. The solvent was removed to obtain Sb (btsa) 3 as a yellow liquid. Sb (btsa) 3 [5.3 g, 8.8 mmol] was added to a 125 ml Schlenk flask containing hexane (50 ml), and dmampH [1-dimethylamino-2-methyl-2- was dissolved in hexane (20 ml). Propanol, 3.09 g, 26.4 mmol] was added slowly. This mixed solution was stirred for one day and the solvent was removed under reduced pressure. The resultant colorless liquid was purified (120 ° C / 10-2 Torr) to obtain an antimony compound bonded with three amino alkoxides represented by the formula (1) as a colorless liquid (3.0 g, yield 72.8%).

Proton nuclear magnetic resonance spectroscopy (1H NMR) analysis results of the antimony precursor synthesized in Example 1 in Figure 1, carbon atom nuclear magnetic resonance spectroscopy (13C NMR) analysis results in Figure 2, thermogravimetric analysis (TGA) and Differential thermal analysis (DTA) results are shown in FIG. 3. From FIG. 3, the Sb (dmamp) 3 compound undergoes a sharp weight loss at 180 ° C. or lower. The residual amount is 13% at 288 ° C. The results of the antimony compound prepared in Example 2 were also the same.

Example 3: Synthesis of Tris [1-dimethylamino-2-methyl-2-butoxy] antimony [Sb (dmamb) 3] III

To a 125 mL Schlenk flask, SbCl 3 [2.0 g, 8.8 mmol] and Na (dmamb) [1-dimethylamino-2-methyl-2-butoxy sodium, 4.03 g, 26.3 mmol] were added followed by hexane (100 mL). Was added. The mixed solution was stirred for one day, the solution was filtered, and then the solvent was removed under reduced pressure, and the pale yellow liquid obtained was purified by vacuum distillation (160 ° C / 10-2 Torr) to combine antimony with three amino alkoxides represented by the formula (1). The compound was obtained as a pale yellow liquid. (3.1 g, yield 69.1%).

1 H NMR (C6D6, 300.13 MHz): 1.09, (t, 3H, CCH2CH3), 1.40 (bs, 3H, CCH3), 1.71, 1.83 (m, 2H, CCH2CH3), 2.23 (s, 6H, N (CH3) 2 ), 2.45 (m, 2H, NCH 2 C).

13 C NMR (C6D6, 75.47 MHz): 9.6, 29.4, 38.0, 47.3, 69.5, 76.3.

Example 4 Synthesis of Tris [1-dimethylamino-2-methyl-2-butoxy] antimony [Sb (dmamb) 3] IV

In a 125 mL Schlenk flask containing hexane (50 mL), Sb (btsa) 3 [5.3 g, 8.8 mmol] was added and dmambH [1-dimethylamino-2-methyl-2- dissolved in hexane (20 mL). Butanol, 3.46 g, 26.4 mmol] was added slowly. The mixed solution was stirred for one day, and the light yellow liquid obtained by removing the solvent under reduced pressure was purified (160 ° C / 10-2 Torr) to obtain an antimony compound having three amino alkoxides represented by the formula (1) as a pale yellow liquid. (2.9 g, yield 64.6%).

Proton nuclear magnetic resonance spectroscopy (1H NMR) analysis results of the antimony precursor synthesized in Example 3 is shown in Figure 4, carbon atom nuclear magnetic resonance spectroscopy (13C NMR) analysis results in Figure 5, thermogravimetric analysis (TGA) and Differential thermal analysis (DTA) results are shown in FIG. 6. Sb (dmamb) 3 compounds undergo rapid weight loss below 130 ° C. The residual amount is 19% at 309 ° C. The results of the antimony compound prepared in Example 4 were also the same.

The antimony (III) amino alkoxide compound, which is an organic antimony trivalent compound prepared from Examples, was found to have very good solubility in organic solvents such as diethyl ether, tetrahydrofuran, toluene and hexane as a liquid at room temperature. As such, the high volatility of the compounds of the present invention and the excellent solubility in organic solvents satisfy the coordination number of the antimony ions by the three amino alkoxide ligands coordinating to the antimony trivalent ions. In addition, two alkyl groups in the alpha carbon position and two methyl groups substituted at the nitrogen atom of the amine effectively mask oxygen and nitrogen, thereby reducing intermolecular interactions and increasing affinity for organic solvents. .

Preparation Example of Antimony Thin Film

Example 5

As a substrate to which the ALD process was applied, a substrate in which a silicon dioxide layer was formed on Si was used.

After the substrate was supplied into the chamber, the temperature of the substrate was raised to 60 ° C., and the temperature of the substrate was maintained at 60 ° C. until the reaction was completed.

After the substrate was fed, tris [1-dimethylamino-2-methyl-2-propoxy] antimony was fed into the chamber with argon (50 sccm) as the source gas.

Tris [1-dimethylamino-2-methyl-2-propoxy] antimony was supplied followed by a plasma at 20W.

Hydrogen gas (200 sccm) was fed into the chamber after plasma injection, followed by argon gas (200 sccm) into the chamber.

After argon gas was supplied disilyl telluride was fed into the chamber along with argon gas (50 sccm).

After supplying disilyl telluride, the plasma was supplied at 20W.

The pressure was maintained at 1 Torr in the entire process, and the exhaust process was performed to remove the reaction by-products after the whole process was completed.

The thickness of the antimony-telluride (Sb ₂ Te ₃ ) thin film formed on the substrate in the chamber was 60 nm and the growth rate was 0.4 nm per cycle. SEM photographs of the prepared thin films are shown in FIG. 8A.

Example 6

A thin film of Sb ₂ Te ₃ was prepared in the same manner as in Example 5, except that the substrate was reacted at 80 ° C. in Example 5.

The thickness of the prepared Sb ₂ Te ₃ thin film was 60nm, the growth rate was 0.4nm per cycle. SEM pictures of the prepared thin film are shown in FIG. 8B.

Example 7

A thin film of Sb ₂ Te ₃ was prepared in the same manner as in Example 5, except that the substrate was reacted at 100 ° C. in Example 5.

The thickness of the prepared Sb ₂ Te ₃ thin film was 80nm, the growth rate was 0.53nm per cycle. SEM photographs of the prepared thin films are shown in FIG. 8C.

{evaluation}

For the antimony-telluride thin films prepared according to Examples 5 to 7, the correlation between the growth rate and the growth temperature is shown in FIG.

Referring to FIG. 7, it can be seen that the growth rate is 0.4 nm per cycle when the temperature of the substrate during manufacture is within the range of 60 ° C to 80 ° C. On the other hand, it can be seen that in the range of 80 ° C to 100 ° C, the growth rate also increases as the temperature rises. That is, in the low temperature section of 60 ℃ to 80 ℃, it was confirmed that a constant ALD window with a low growth rate.

Referring to the SEM photographs shown in FIGS. 8A to 8C, when the SEM photographs of the thin film of Sb ₂ Te ₃ grown at low temperatures, it can be seen that a generally flat surface is formed, in particular, relatively low temperatures (60 ° C.) In the case of the thin film deposited in (Fig. 8a) it can be seen that the case has a flatter surface than when deposited at 100 ° C (Fig. 8c).

Figure 9 shows the analysis of the XRD diffraction pattern of the thin film prepared by Examples 5-7. Referring to FIG. 9, a thin film of polycrystalline Sb ₂ Te ₃ was identified in all temperature ranges regardless of the temperature ranges shown in Examples 5 to 7, and thus, the Sb ₂ Te ₃ thin film of Sb ₂ Te ₃ by the ALD process was observed in the temperature range. It can be seen that the low temperature deposition of the thin film is possible.

In the above description of the present invention with reference to an embodiment of the present invention and the accompanying drawings, the terms or words used in the present specification and claims should not be construed as being limited to the ordinary or dictionary meanings, the inventors In order to explain the invention in the best way, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the concept of terms can be properly defined.

Claims (14)

1. An antimony amino alkoxide compound represented by the following formula (1):

   <Formula 1>

   Sb [O-A-NR1R2] 3

   In Chemical Formula 1,

   A is C2-C5 alkylene unsubstituted or substituted with a C1-C10 linear or branched alkyl group;

   R1 and R2 are each independently a C1-C10 linear or branched alkyl group.
2. The method of claim 1,

   The compound represented by Formula 1 is an antimony amino alkoxide compound, characterized in that the compound represented by the formula (2).

   <Formula 2>

   Sb [O-CR3R4 (CH2) m-NR1R2] 3

   In Chemical Formula 2,

   R 3 and R 4 are each independently C 1 -C 10 linear or branched alkyl groups;

   m is an integer of 1-3.
3. The method of claim 2,

   In Chemical Formula 2,

   R 1, R 2, R 3 and R 4 are each independently methyl, ethyl, n-propyl, i-propyl or t-butyl;

   Antimony amino alkoxide, characterized in that m is 1 or 2.
4. A method for preparing an antimony amino alkoxide compound represented by Formula 1, comprising reacting an antimony halide compound represented by Formula 3 with an alkali metal salt of an alcohol represented by Formula 4:

   <Formula 1>

   Sb [O-A-NR1R2] 3

   <Formula 3>

   SbX3

   <Formula 4>

   M [O-A-NR1R2]

   In Formula 1, Formula 3 and Formula 4,

   A is C2-C5 alkylene unsubstituted or substituted with a C1-C10 linear or branched alkyl group;

   R 1 and R 2 are, independently from each other, a C 1 -C 10 linear or branched alkyl group;

   M is Li, Na or K;

   X is Cl, Br or I.
5. Preparing an antimony compound represented by Chemical Formula 6 by reacting an antimony halide compound of Chemical Formula 3 with an alkali metal compound represented by Chemical Formula 5 under an organic solvent; And

   Reacting the antimony compound represented by the formula (6) and the alcohol represented by the formula (7) in an organic solvent

   Method for producing an antimony amino alkoxide compound of Formula 1, comprising:

   <Formula 1>

   Sb [O-A-NR1R2] 3

   <Formula 3>

   SbX3

   <Formula 5>

   M [NR52]

   <Formula 6>

   Sb [NR52] 3

   <Formula 7>

   HO-A-NR1R2

   In Chemical Formula 1, Chemical Formula 3, Chemical Formula 5, Chemical Formula 6, and Chemical Formula 7,

   A is C2-C5 alkylene unsubstituted or substituted with a C1-C10 linear or branched alkyl group;

   R 1 and R 2 are each independently C 1 -C 10 linear or branched alkyl groups;

   R5 is a C1-C10 linear or branched alkyl group, or SiR63, and R6 is a C1-C10 linear or branched alkyl group;

   M is Li, Na or K;

   X is Cl, Br or I.
6. Preparing a substrate in a vacuum chamber;

   Preparing an antimony precursor material;

   Preparing a source gas from the antimony precursor material;

   Preparing a reaction gas including hydrogen gas;

   Preparing a purge gas;

   Preparing a metal precursor gas from the metal precursor material; And

   And performing a one-cycle process of sequentially supplying the source gas, the reaction gas, the purge gas, and the metal precursor gas into the vacuum chamber to form an antimony-metal monolayer layer thin film on the substrate.

   The antimony precursor material is a method for producing an antimony thin film, characterized in that the antimony amino alkoxide represented by the following formula (1):

   <Formula 1>

   Sb [OA-NR ¹ R ² ] ₃

   Wherein A is C ₂ to C ₅ alkylene unsubstituted or substituted with a C ₁ to C ₁₀ linear or branched alkyl group;

   R ¹ and R ² are each independently a C ₁ to C ₁₀ linear or branched alkyl group.
7. The method of claim 6,

   And repeatedly forming the antimony-metal monolayer layer on the substrate to control the thickness of the thin film.
8. The method of claim 6,

   The substrate is a method for producing an antimony thin film, characterized in that maintained in the temperature range of 60 ℃ to 160 ℃.
9. The method of claim 6,

   The purge gas is an argon thin film manufacturing method, characterized in that the argon.
10. The method of claim 6,

    The metal is telluride manufacturing method of the antimony thin film, characterized in that.
11. The method of claim 6,

    In the one-cycle process of sequentially blowing the source gas, reaction gas, purge gas and the metal precursor gas into the vacuum chamber, the step of blowing the source gas and further blowing a first plasma, and the metal precursor And further blowing a second plasma after blowing the gas, further comprising a further antimony thin film.
12. The method of claim 6,

    The antimony precursor is a method for producing an antimony thin film, characterized in that the compound represented by the formula (2).

    <Formula 2>

    Sb [O-CR ³ R ⁴ (CH ₂ ) m-NR ¹ R ² ] ₃

    In Chemical Formula 2,

    R ³ and R ⁴ are each independently C ₁ -C ₁₀ linear or branched alkyl groups;

    m is an integer of 1-3.
13. The method of claim 12,

    In Chemical Formula 2,

    R ¹ , R ² , R ³ and R ⁴ are each independently methyl, ethyl, n-propyl, i-propyl or t-butyl;

    M is 1 or 2, characterized in that the antimony thin film manufacturing method.
14. An antimony thin film produced by the method according to any one of claims 6 to 13.

Images